Asymmetric synthesis of alkyl chrysanthemates

ABSTRACT

Process for producing an optically active alkyl chrysanthemate by reacting 2,5-dimethyl-2,4-hexadiene with an alkyl diazoacetate in the presence of a copper complex coordinated with a particular Schiff base.

This is a continuation-in-part of copending application Ser. No. 442,413filed Feb. 14, 1974.

The present invention is a process for producing an optically activealkyl chrysanthemate wherein 2,5-dimethyl-2,4-hexadiene is reacted withan alkyl diazoacetate in the presence of a copper complex coordinatedwith a novel kind of Schiff base.

Chrysanthemic acid is an important material for synthetic pyrethroidswhich are effective as insecticides. There are four stereoisomers ofchrysanthemic acid: two kinds of geometric isomers, i.e. cis and trans,each including d and l optical isomers. Among them, the pyrethroidsderived from d-trans and d-cis chrysanthemic acids are known to beparticularly effective in insecticidal power. In this connection,naturally occurring chrysanthemic acid is known to have d-transstructure.

There can be two industrial methods for obtaining optically activechrysanthemic acid. One is to synthesize a racemic mixture first, whichis subsequently subjected to optical resolution, and the other method isdirect asymmetric synthesis.

One of the synthetic processes of chrysanthemic acid is to react analkyl diazoacetate with 2,5-dimethyl-2,4-hexadiene in the presence of acopper catalyst (see Great Britain Pat. No. 740,014) and then tohydrolyze the resulting alkyl chrysanthemate.

This invention relates to the asymmetric synthesis of alkylchrysanthemates. In our Belgian Pat. No. 787,473. there is described andclaimed a process for producing an optically active alkyl chrysanthemateby reacting an alkyl diazoacetate with 2,5-dimethyl-2,4-hexadiene in thepresence of a copper catalyst coordinated with a chiral ligand accordingto the following equation: ##STR1## wherein L* is a chiral ligand.

We have now found, according to the present invention that it isadvantageous to catalyze the asymmetric synthesis of alkylchrysanthemates with novel copper complex coordinated with a novel kindof chiral Schiff base having the following formula: ##STR2## wherein C*is an asymmetric carbon atom, R¹ is selected from the group consistingof (a) alkyl groups whose carbon atom number is 1- 10, and (b) aralkylgroups with or without alkoxy substituent(s), whose total carbon atomnumber is 7- 20, R² is selected from aryl groups with alkoxysubstituent(s), whose total carbon atom number is 7- 30, X is selectedfrom the group consisting of (a) hydrogen atom, (b) alkyl groups having1- 10 carbon atoms, (c) phenyl group, (d) benzo group, (e) alkoxy groupshaving 1- 10 carbon atoms, (f) halogen atoms and (g) nitro group, and Yis a hydrogen atom. That is, the present invention relates to a processfor producing an optically active alkyl chrysanthemate by reacting2,5-dimethyl-2,4-hexadiene with an alkyl diazoacetate in the presence ofsaid chiral copper complex.

In the following a further explanation will be given on the chiralcopper complexes used as catalysts in the present invention.

When the Schiff base of the formula (I) forms a metal complex withdivalent copper ion, two kinds of chelate are possible. (for thechemistry of metal complexes of Schiff bases, see R. H. Holm, G. W.Everett, Jr., and A. Chakravorty "Progress in Inorganic Chemistry" 7,83-214, (1966), Interscience Publishers, New York)

One has the following dimeric structure (II) wherein the Schiff basebehaves as tridentate ligand: ##STR3## wherein R¹, R², X and Y are asdefined above. The other has the following monomeric structure (III)wherein the Schiff base behaves as bidentate ligand: ##STR4## whereinR¹, R², X and Y are as defined above. (for the copper complexes ofN-salicylidene-2-aminoethanol, see R. P. Houghton and D. J. Pointer, J.Chem. Soc. 4214 (1965))

The binuclear copper complex of the formula (II) used as catalyst in thepresent invention is prepared by the reaction of a Schiff base of theformula (I) with a cupric salt such as cupric acetate etc. Themononuclear copper complex of the formula (III) is simply obtained bythe reaction of an amino alcohol having the following defined formula(IV) and a bis(salicylaldehydato) copper or a derivative thereof.

The chiral Schiff base of the formula (I) is synthesized by the reactionof a chiral amino alcohol having the formula (IV) with asalicyclaldehyde derivative having the formula (v): ##STR5## wherein R¹,R², X and Y are as defined above.

Specific examples of the substituent R¹ in the amino alcohol (IV) ismethyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-butyl, -t-butyl,hexyl, octyl, cyclohexyl, cyclohexylmethyl, phenyl, benzyl, benzhydryl,2,2-diphenylethyl, tolyl, α-naphthyl and β-naphthyl. Among theseexamples, preferred substituents of R¹ are methyl, isopropyl, isobutyl,cyclohexylmethyl, benzyl and a benzyl group having a substituent at the4-position of the aromatic nucleus, of which the substituent is, forexample, methoxy, ethoxy, propoxy, isopropoxy, butoxy, hexyloxy,octyloxy, or benzyloxy, etc. As R² in the amino alcohol, a phenyl grouphaving a substituent at the 2-position or having substituents at the2,5-positions is preferred. Specific examples of 2-substituted phenylgroups are 2-methoxyphenyl, 2-ethoxyphenyl, 2-propoxyphenyl,2-isopropoxyphenyl, 2-butoxyphenyl, 2-t-butoxyphenyl, 2-hexyloxyphenyl,2-octyloxyphenyl, 2-henzyloxyphenyl, 2-phenoxyphenyl, etc. Specificexamples of 2,5-substituted phenyl groups are 2-methoxy-5-methylphenyl,2-butoxy-5-methylphenyl, 5-methyl-2-octyloxyphenyl,2-benzyloxy-5-methylphenyl, 5-t-butyl-2-methoxyphenyl,2-butoxy-5-t-butylphenyl, 5-t-butyl-2-octyloxyphenyl,2-benzoxy-5-t-butylphenyl, 4-methoxybiphenyl-3-yl,4-butoxybiphenyl-3-yl, 4-octyloxybiphenyl-3-yl,4-benzyloxybiphenyl-3-yl, 2,5-dimethoxyphenyl, 2,5-dibutoxyphenyl,2,5-dioctyloxyphenyl, 2,5-dibenzyloxyphenyl, etc.

The optically active amino alcohols of the formula (IV) to be used inthis invention may be prepared in any of the following two ways, ie..one is to optically resolve a racemic mixture of the correspondingalcohol with a proper optical resolution agent, and the other is toderive the same from the corresponding optically active precursor. Thus,for example, when an optically active amino acid ester of the followingformula (VI) is reacted with a Grignard reagent of the following formula(VII) there is obtained the optically active amino alcohol (IV):##STR6## wherein R¹, R² is alkyl, aryl, or aralkyl, R³ is alkyl orbenzyl of 1- 10 carbon atoms and Z is chlorine, bromine or iodine. Asfor the addition reaction of phenyl magnesium bromide to (L)-alanineethyl ester, references may be made for example to A. McKenzie, R.Roger, G. O. Willis, J. Chem. Soc., 779 (1926) and B. M. Benjamin, H. J.Schaefer, C. J. Collins, J. Am. Chem. Soc. 79, 6160 (1957).

Further, the substituent X in the salicylaldehyde derivativ (V) employedin the synthesis of the chiral Schiff base is a hydrogen atom, alkylgroup, aralkyl group, aryl group, or a substituent containing ahetero-atom, and the substituent Y is a hydrogen atom, alkyl group,aralkyl group, or aryl group.

Specific examples of the reactive substituents containing (a)hetero-atom(s) are OH, OR, OCOR, CHO, COR, COOH, COOR, CN, CONH₂,NH₂,NHR, NR₂, NHCOR, NO₂, SH, SR, SOR, SO₂ R, SO₃ H, SO₃ R, a halogenatom, etc. wherein R is alkyl, aralkyl or aryl.

Specific examples of the salicylaldehyde derivatives (V) aresalicyclaldehyde, 3ethoxylsalicylaldehyde, O-vanilline,3,5-dibromosalicylaldehyde, 5-chlorosalicylaldehyde,3-nitrosalicylaldehyde, 3-isopropyl-6-methylsalicylaldehyde,2-hydroxyl-naphthaldehyde, 1-hydroxy-2-naphthaldehye and the like.

Among the chiral copper complexes employed as catalysts in the presentinvention, specific examples of the binuclear copper complexes (II) arethose that are derived from the following chiral Schiff bases:

(a)N-salicylidene-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl-1-propanol,

(b)N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butylpheny)-3-phenyl-1-propanol

(c) N-salicylidene-2-amino- 1,1-di(2-methoxyphenyl)-3-phenyl-1-propanol,

(d) N-salicylidene-2-amino-1,1-di(2-ethoxyphenyl)-3-phenyl-1-propanol,

(e) N-salicylidene-2-amino-1,1-di(2-butoxyphenyl)-3-phenyl-1-propanol,

(f) N-salicylidene-2-amino-1,1-di(2-octyloxyphenyl)-3-phenyl-1-propanol,

(g) N-salicylidene-2-amino-1,1-di(2-phenoxyphenyl)-3-phenyl-1-propanol,

(h)N-salicylidene-2-amino-1,1-di(2-benzyloxy-5-methylphenyl)-3-phenyl-1-propanol,

(i)N-salicylidene-2-amino-1,1-di(5-t-butyl-2-isopropoxyphenyl)-3-phenyl-1-propanol,

(j)N-salicylidene-2-amino-1,1-di(5-t-butyl-2-octyloxyphenyl)-3-phenyl-1-propanol,

(k)N-salicylidene-2-amino-1,1-di(4-butoxybiphenyl-3-yl)-3-phenyl-1-propanol,

(l)N-salicylidene-2-amino-1,1-di(2,5-dibutoxyphenyl)-3-phenyl-1-propanol,

(m)N-salicylidene-2-amino-1,1-di(2-isopropoxyphenyl)-3-(4-isopropoxyphenyl)-1-propanol,

(n)N-salicylidene-2-amino-1,1-di(5-t-butyl-2-octyloxyphenyl)-3-(4-isopropoxyphenyl)-1-propanol,

(o)N-salicylidene-2-amino-1,1-di(2-butoxyphenyl)-3-cyclohexyl-1-propanol,

(p) N-salicylidene-2-amino-2,2-di(2-methoxyphenyl)-4-methyl-1-pentanol,

(q)N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butylphenyl)-4-methyl-1-pentanol,

(r)N-salicylidene-2-amino-1,1-di(2-benzyloxy-5-t-butylphenyl)-4-methyl-1-pentanol,

(s) N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butylphenyl)-1-propanol,

(t) N-salicylidene-2-amino-1,1-di(2-butoxyphenyl)-3-methyl-1-butanol,

(u) N-salicylidene-2-amino-1,1-di(2-butoxyphenyl)-1-propanol,

(v)N-(3,5-dibromosalicylidene)-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl-1-propanol,

(w)N-(3-ethoxysalicylidene)-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl-1-propanol,

(x)N-(2-hydroxy-1-naphthylmethylene)-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl-1-propanol,or

(y) N-salicylidene-2-amino-1,1-di(4-butoxybiphenyl-3-yl)-1-propanol.

Specific examples of the mononuclear copper complexes (III) are thosethat are derived from the following chiral Schiff bases:

(a) N-salicylidene-2-amino-1,1-di(2-methoxyphenyl)-3-phenyl-1-propanol.

(b) N-salicylidene-2-amino-1,1-di(3-methoxyphenyl)-3-phenyl-1-propanol,or

(c) N-salicylidene-2-amino-1,1-di(2-methoxyphenyl)-4-methyl-1-pentanol.

In the actual practice of the present invention, the reaction can becarried out regardless of whether the chiral copper complex employed ascatalyst is soluble or insoluble in the reaction system.

The catalyst may be recovered and purified by appropriate method forrepeated uses.

Preferably, the molar ratio of the copper complex to alkyl diazoacetateis in a range of 0.001- 0.1.

There is no particular restriction on the choice of the alcoholic partof the alkyl diazoacetate used in the reaction of the present invention,though normally lower aliphatic alcohols having 1 to 8 carbon atoms areemployed.

The reaction of the present invention can be carried out either in theabsence or presence of a solvent.

Although the reaction temperature is not particularly limited, usually atemperature between -50° C. and 150° C. is suitable. In particular casesof carrying out the reaction at a temperature below the melting point of2,5-dimethyl-2,4-hexadiene (15° C.), a suitable solvent may be desirablyadded to the reaction system. Aromatic hydrocarbons such as bensene,toluene and xylene are suitable solvents in such cases.

The present invention is explained in further detail by the example setforth below. They are not, however, to be taken as being limitativethereof.

In general unequivocal coorelation exists between the absoluteconfiguration of the substance which induces the asymmetry and that ofthe substance to which the asymmetry is induced. Therefore, in thisinvention, too, it is needless to say that when the enatiomeric coppercomplex of the one described in the following examples is used as thecatalyst, the resulting alkyl chrysanthemate and chrysanthemic acid willalso have the enanthiomeric structure.

EXAMPLE 1

An amount of 0.47 g. (0.4 millimol) of the binuclear copper complex of(R)-N-salicylidene-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl-1-propanol(corresponding to the formula (II) wherein R¹ = benzyl, R² =2-isopropoxyphenyl, and X= Y= hydrogen) was dissolved in 8.8 g. (80millimols) of 2,5-dimethyl-2,4-hexadiene. To this solution, a mixture of8.8 g. (80 millimols) of the above-mentioned diene and 4.6 g. (40millimols) of ethyl diazoacetate was added dropwise under stirring overa period of 6 hours. At the beginning of the addition, the reactionsystem was once heated to 70° C. to facilitate the decomposition ofdiazoacetate and thereafter the temperature was maintained at 40° C. Atthe end of the addition, evolution of a nearly quantitative amount ofnitrogen gas was observed.

From the reaction mixture, unreacted excess diene (boiling point: 40°C./20 mmHg) was distilled off under reduced pressure, and 4.1 g. ofethyl chrysanthemate was obtained as an oil having a boiling point of60° C./0.5 mmHg, the yield being 53% with respect to the diazo compound.

This sample represented an optical rotation α_(D) of +8.80° (neat, 1 dm)and the ratio of cis/trans isomer of the ethyl chrysanthemate was 42/58(as determined by gas chromatography).

Chrysanthemic acid was obtained by the hydrolysis of this ester. Theacid, after distillation, represented specific optical rotation [α]_(D)of +25.48° (c 5.07, chloroform). Gas chromatographic analysis showedthat the composition of the four optical isomers of this sample was asfollows:

d-trans isomer: 43.0 %,

d-cis isomer: 30.3 %,

l-trans isomer: 16.1%,

l-cis isomer: 10.6 %.

(for the analytical method, see A. Murano, Agr. Biol. Chem., 36, 2203(1972) )

EXAMPLE 2

A similar reaction to Example 1 was carried out using 0.58 g. of thecopper complex of(R)-N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butylphenyl)-3-phenyl-1-propanol(corresponding to the formula (II) wherein R¹ = benzyl, R² =2-butoxy-5-t-butylphenyl, and X= Y= hydrogen) to give 4.0 g. of ethylchrysanthemate. Reaction temperature, 40° C.; chemical yield, 52 %;cis/trans ratio, 43/57; and optical rotation, α_(D) +10.26 (neat, 1 dm).The chrysanthemic acid was obtained by the hydrolysis of this ester toshow specific optical rotation [α]_(D) of +29.84° (c 5.12, chloroform).The composition of the optical isomers was as follows:

d-trans isomer: 49.7 %,

d-cis isomer: 33.8 %,

l -trans isomer: 10.6%,

l -cis isomer: 10.9 %.

EXAMPLES 3 to 41

In a similar manner to Example 1, optically active ethyl chrysanthemateand chrysanthemic acid were synthesized, using other kinds of chiralbinuclear copper complexes of the formula (II). The results aresummarized in Table I.

                                      Table 1                                     __________________________________________________________________________    Asymmetric synthesis with binuclear copper complexes                          __________________________________________________________________________                                                    Chrysanthemic                                                  Ethyl Chrysanthemate                                                                         acid                                              Copper                                                                             Tolu-                                                                             Temp.                                                                             Chem.     αD                           Exam-               complex                                                                            ene     yield     (neat)                                                                             [α].sub.D               ple Chiral Schiff base                                                                            (g.) (ml.)                                                                             (° C.)                                                                     (%) cis/trans                                                                           (1 dm)                                                                             (Chloroform)                  __________________________________________________________________________        (S)-N-salicylidene-                                                       3   2-amino-1,1-di(2-                                                                             0.42 0   40  58  38/62 -8.01                                                                              -23.10                            methoxyphenyl)-3-                                                             phenyl-1-propanol                                                             (S)-N-salicylidene-                                                       4   2-amino-1,1-di(2-                                                                             0.45 0   50  58  38/62 -8.65                                                                              -21.70                            ethoxyphenyl)-3-                                                              phenyl-1-propanol                                                             (S)-N-salicylidene-                                                       5   2-amino-1,1-di(2-                                                                             0.50 0   50  69  39/61 -8.80                                                                              -24.50                            butoxyphenyl)-3-                                                              phenyl-1-propanol                                                             (R)-N-salicylidene-                                                       6   2-amino-1,1-di(2-                                                                             0.58 0   40  65  38/62 +9.03                                                                              +26.86                            octyloxyphenyl)-3-                                                            phenyl-1-propanol                                                             (R)-N-salicylidene-2-                                                     7   amino-1,1-di(2-pheno-                                                                         0.56 0   40  56  33/67 +5.28                                                                              --                                xyphenyl)-3-phenyl-                                                           1-propanol                                                                    (S)-N-salicylidene-                                                           2-amino-1,1-di(2-                                                         8   benzyloxy-5-methyl-                                                                           0.57 10  40  61  42/58 -8.93                                                                              --                                phenyl)-3-phenyl-                                                             1-propanol                                                                    (S)-N-salicylidene-                                                           2-amino-1,1-di(5-                                                         9   t-butyl-2-isopro-                                                                             0.56 0   40  59  39/61 -10.88                                                                             -30.06                            poxy-phenyl)-3-                                                               phenyl-1-propanol                                                             (R)-N-salicylidene-                                                       10  2-amino-1,1-di(5-t-butyl-                                                     2-octyloxyphenyl)-                                                                            0.67 0   40  60  43/57 +10.17                                                                             +30.29                            3-phenyl-1-propanol                                                           (R)-N-salicylidene-                                                           2-amino-1,1-di(4-                                                         11  butoxybiphenyl-3-                                                                             0.61 0   40  59  40/60 +8.64                                                                              --                                yl)-3-phenyl-1-                                                               propanol                                                                      (R)-N-salicylidene-                                                       12  2-amino-1,1-di(2,5-                                                                           0.59 0   40  63  38/62 +10.65                                                                             --                                dibutoxyphenyl)-3-                                                            phenyl-1-propanol                                                             (S)-N-salicylidene-                                                           2-amino-1,1-di(2-iso-                                                     13  propoxyphenyl)-3-(4-                                                                          0.52 0   40  55  39/61 -10.81                                                                             --                                isopropoxyphenyl)-                                                            1-propanol                                                                    (S)-N-salicylidene-2-amino-                                                   1,1-di(5-t-butyl-                                                         14  2-octyloxyphenyl)-                                                                            0.72 0   40  51  41/59 -11.41                                                                             -34.65                            3-(4-isopropoxy-                                                              phenyl)-1-propanol                                                            (S)-N-salicylidene-                                                       15  2-amino-1,1-di(2-buto-                                                                        0.50 0   40  53  35/65 -8.89                                                                              --                                xyphenyl)-3-cyclo-                                                            hexyl-1-propanol                                                              (S)-N-salicylidene-                                                       16  2-amino-1,1-di(2-                                                                             0.40 0   40  54  41/59 -5.78                                                                              --                                methoxyphenyl)-4-                                                             methyl-1-pentanol                                                             (S)-N-salicylidene-                                                           2-amino-1,1-di(2-                                                         17  butoxy-5-t-butyl-                                                                             0.64 0   40  47  42/58 -5.65                                                                              --                                phenyl)-4-methyl-                                                             1-pentanol                                                                    (S)-N-salicylidene-                                                           2-amino-1,1-di(2-                                                         18  benzyloxy-5-t-  0.62 0   40  46  43/57 -5.35                                                                              --                                butylphenyl)-4-                                                               methyl-1-pentanol                                                             (S)-N-salicylidene-                                                       19  2-amino-1,1-di(2-                                                                             0.55 0   40  54  42/58 - 11.58                                                                            -35.84                            butoxy-5-t-butyl-                                                             phenyl)-1-propanol                                                            (S)-N-salicylidene-                                                       20  2-amino-1,1-di(2-                                                                             0.44 0   40  52  42/58 -6.11                                                                              --                                butoxyphenyl)-3-                                                              methyl-1-butanol                                                              (S)-N-salicylidene-                                                       21  2-amino-1,1-di(2-                                                                             0.41 0   40  63  41/59 -9.20                                                                              --                                butoxyphenyl)-1-                                                              propanol                                                                      (R)-N-(3,5-dibromo-                                                           salicylidene)-2-                                                          22  amino-1,1-di(2-iso-                                                                           1.09 0   30  40/60                                                                             +8.77 --                                     propoxyphenyl)-3-                                                             phenyl-1-propanol                                                             (R)-N-(3-ethoxysali-                                                      23  cylidene)-2-amino-1,1-                                                                        0.91 0   30  57  +7.02 --                                     di(2-isopropoxyphenyl)-                                                       3-phenyl-1-propanol                                                           (R)-N-(2-hydroxy-1-                                                           naphthylmethylene)-                                                       24  2-amino-1,1-di(2-                                                                             0.92 0   63  41.59                                                                             +9.55 +25.84                                 isopropoxyphenyl)-                                                            N-salicylidene(S)-                                                            N-salicylidene(S)-                                                        25  2-amino-1,1-di(2,3'-                                                                          0.53 0   5.35                                                                              --  -10.60                                                                              --                                     oxapentoxy-5-t-butyl-                                                         phenyl)-1-propanol                                                            N-salicylidene(S)-                                                            2-amino-1,1-di(2-                                                         26  cyclohexyloxy-5-t-                                                                            0.56 0   40  58  --    -9.63                                                                              --                                butylphenyl)-1-                                                               propanol                                                                      N-salicylidene(R)-                                                            2-amino-1,1-di(2-                                                         27  cyclohexyloxy-5-                                                                              0.60 0   40  60  --    +9.92                                                                              --                                t-butylphenyl)-3-                                                             41/59                                                                       N-salicylidene(S)-                                                          28  2-amino-1,1-di(2-                                                                             1.05 0   40  60  42/58 -8.88                                                                              --                                t-butoxy-5-t-butyl-                                                           phenyl)-1-propanol                                                            N-salicylidene(S)-                                                        29  2-amino-1,1-di(2-iso-                                                                         0    40  46  41/59                                                                             -7.16 --                                     propoxy-5-methyl-                                                             N-salicylidene(S)-                                                            N-salicylidene(S)-                                                            2-amino-1,1-di(2-                                                         30  benzyloxy-4-t-  0.56 0   40  58  43/57 -5.70                                                                              -16.79                            butylphenyl)-1-                                                               propanol                                                                      N-salicylidene(S)-                                                            2-amino-1,1-di(2-                                                         31  sec-butoxy-5-t- 0.60 0   40  51  41.59 -7.40                                                                              -21.24                            butylphenyl)-1-                                                               propanol                                                                      N-salicylidene(S)-                                                            2-amino-1,1-di(2-                                                         32  benzyloxy-5-t-  0.56 0   40  57  42/58 - 7.27                                                                             --                                butylphenyl)-1-                                                               propanol                                                                      N-salicylidene(S)-2-                                                      33  amino-1,1-di(2-butoxy-                                                                        0.52 0   40  56  48/52 - 8.20                                                                             --                                4-t-butylphenyl)-1-                                                           propanol                                                                      N-salicylidene(S)-                                                        34  2-amino-1,1-di(2,5-                                                                           0.53 0   40  63  40/60 - 6.72                                                                             --                                dibutoxyphenyl)-                                                              1-propanol                                                                    N-salicylidene(S)-                                                        35  2-amino-1,1-di(4-                                                                             0.50 0   40  59  38/62 - 5.35                                                                             --                                octyloxy-3-biphenyl)-                                                         1-propanol                                                                    N-salicylidene(S)-                                                        36  2-amino-1,1-di(4-                                                                             0.56 0   40  66  42/58 -11.28                                                                             -31.69                            butoxy-3-biphenyl)-                                                           1-propanol                                                                    N-salicylidene(S)-                                                        37  2-amino-1,1-di(5-                                                                             0.60 0   40  54  49/51 -13.52                                                                             -38.76                            t-butyl-2-ocyloxy-                                                            phenyl)-1-propanol                                                            N-salicylidene(S)-                                                        38  2-amino-1,1-di(2-                                                                             0.45 0   40  60  41/59 - 7.22                                                                             -20.46                            butoxy-5-methylphenyl)-                                                       1-propanol                                                                    N-salicylidene(S)-                                                            2-amino-1,1-di(2-                                                         39  butoxy-5-t-butyl-                                                                             0.66 0   40  57  --    - 9.70                                                                             -29.92                            phenyl)-3-(4-benzyl-                                                          oxyphenyl)-1-pro-                                                             panol                                                                         N-salicylidene(S)-                                                            2-amino-1,1-di(2-                                                         40  butoxy-5-t-butyl-                                                                             0.55 0   40  59  --    - 9.67                                                                             -24.60                            phenyl)-3-methyl-1-                                                           butanol                                                                       N-salicylidene(S)-                                                        41  2-amino-1,1-di(2-                                                                             0.46 0   40  58  --    - 5.88                                                                             -17.31                            butoxyphenyl)-4-                                                              methyl-1-pentanol                                                         __________________________________________________________________________

EXAMPLE 42

An amount of 1.20 g. (1.2 millimols) of the mononuclear cooper complexof(R)-N-salicylidene-2-amino-1,1-di(2-methoxyphenyl)-3-phenyl-1-propanol(corresponding to the formula (III) wherein R¹ = benzyl, R² =methoxyphenyl, and X= Y== hydrogen) was dissolved in a mixture of 60 ml.toluene and 13.2 g. (120 millimols) 2,5-dimethyl2,4-hexadiene. To thissolution, a mixture of 13.2 g. (120 millimols) of the above-mentioneddiene and 4.6 g. (40 millimols) of ethyl diazoacetate was added dropwiseunder stirring over a period of 11 hours. At the beginning of theaddition, the reaction system was once heated to 85° C. and thereafterthe temperature was maintained at 0° C. At the end of the addition,nearly quantitative amount of nitrogen gas was evolved.

On distilling off unreacted excess diene under reduced pressure, 3.7 g.of ethyl chrysanthemate (yield: 47 % with respect to the diazo compound)was obtained. This ester represented an optical rotation α_(D) of +10.4°(neat, 1 dm), and the ratio of cis/trans isomer was 38/62 (as determinedby gas chromatography).

The chrysanthemic acid was obtained by the hydrolysis of the ester toshow a specific optical rotation [α]_(D) of +27.78° (c 5.49,chloroform). This product was analyzed for the four optical isomers bygas chromatography. The results were as follows:

d-trans isomer: 46.7 %,

d-cis isomer: 29.4 %,

l -trans isomer: 14.6 %,

l -cis isomer: 9.3 %.

EXAMPLES 43 and 44

In a similar manner to Example 25, optically active ethyl chrysanthemateand chrysanthemic acid were synthesized, using other two kinds ofmononuclear copper complexes of the formula (III). The results aresummarized in Table 2.

                                      Table 2                                     __________________________________________________________________________    Asymmetric synthesis with mononuclear                                         copper complexes                                                              __________________________________________________________________________                                                Chrysanthemic                                                   Ethyl chrysanthemate                                                                        acid                                              Copper                                                                             Tolu-    Chem.     α.sub.D                         Exam-           complex                                                                            ene Temp.                                                                              Yield     (neat)                                                                            [α].sub.D                   ple Chiral Schiff base                                                                        (g.) (ml.)                                                                             (° C.)                                                                      (%) cis/trans                                                                           (1 dm)                                                                            (Chloroform)                      __________________________________________________________________________        (R)-N-salicylidene-                                                       43  2-amino-1,1-di(3-                                                                         0.42 0   40   57  34/66 +3.31                                                                             --                                    methoxyphenyl)-3-                                                             phenyl-1-propanol                                                             (S)-N-salicylidene-                                                       44  2-amino-1,1-di(2-                                                                         0.37 0   40   59  36/64 -9.54                                                                             --                                    methoxyphenyl)-4-                                                             methyl-1-pentanol                                                         __________________________________________________________________________

EXAMPLE 1A

A mixture of 2.5 g. (5.9 millimols) of(R)-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl-1-propanol {[α]_(D)+65.0° (c 1.0, chloroform)} and 0.66 g. (5.4 millimols) ofsalicylaldehyde in 50 ml benzene was heated under reflux for 2.5 hours.After the distillation of the solvent from the reaction mixture, theresidue was recrystallized from ethanol to give(R)-N-salicylidene-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl-1-propanolas yellow crystals. Yield, 2.43 g. (85%); melting point, 152° - 153° C.;[α]_(D), +65.25° (c 1.00, chloroform).

    ______________________________________                                        Elemental analysis for C.sub.34 H.sub.37 NO.sub.4                                           C (%)      H (%)      N (%)                                     Found:        77.81      7.26       2.62                                      Calculated:   77.98      7.12       2.68                                      ______________________________________                                    

EXAMPLE 1B

Two grams (3.82 millimols) of the Schiff base obtained in Example 1A and0.78 g. (3.9 millimols) of cupric acetate monohydrate were dissolved in20 ml. ethanol, and the solution was heated under reflux for 10 minutes.After removal of the solvent from the reaction mixture, the residue wasdissolved in 35 ml. benzene and the solution was washed with a 50 ml.saturated aqueous solution of sodium bicarbonate. The organic layer waswashed with water and dried. After evaporation of the solvent theresulting precipitate was collected by filtration and washed twice with10 ml. methanol. Upon drying the solids under reduced pressure,binuclear copper complex of(R)-N-salicylidene-2-amino-1,1-di(2-isopropoxyphenyl)-1-propanol wasobtained as grayish blue crystals. Yield, 1.93 g. (86 %), [α]₅₄₆, +1360°(c 0.143, benzene), melting point, 178° - 179° C. (decomposed).

    ______________________________________                                        Elemental analysis for C.sub.68 H.sub.70 Cu.sub.2 N.sub.2 O.sub.8                         C (%)     H (%)    N (%)  Cu (%)                                  Found:      69.41     6.06     2.98   11.00                                   Calculated: 69.78     6.03     2.39   10.86                                   Magnetic susceptibility μ = 0.86 B.M.                                      ______________________________________                                    

0.5 g. of the above-mentioned copper complex was dissolved in 10 ml.pyridine. Upon adding 50 ml. water to this solution, bluish white solidsseparated out. When the solids were washed with 10 ml. methanol, amononuclear copper complex containing one mol of pyridine was obtainedas red crystals. Yield, 0.50 g. (88%), [α]₅₄₆, +2320° (c 0.876,benzene), melting point, 186° - 188° C. (decomposed).

    ______________________________________                                        Elemental analysis for C.sub.34 H.sub.35 CuNO.sub.4 . C.sub.5 H.sub.5 N                   C (%)     H (%)    N (%)  Cu (%)                                  Found:      70.65     6.31     4.20   9.77                                    Calculated: 70.51     6.07     4.22   9.57                                    Magnetic susceptibility μ = 1.87 B.M.                                      ______________________________________                                    

EXAMPLES 2A to 41A

In a similar manner to Example 1A, other 40 kinds of chiral Schiff basesof the formula (I) were synthesized from chiral amino alcohols of theformula (IV) and salicylaldehyde derivatives of the formula (V). Theresults are summarized in Table 3.

EXAMPLES 2B to 41B

In a similar manner to Example 1B, other 40 kinds of chiral binuclearcopper complexes of the formula (II) were synthesized from the chiralSchiff bases of the formula (I) and cupric acetate. The results aresummarized in Table 3.

                                      Table 3                                     __________________________________________________________________________    Chiral Schiff bases and binuclear                                             copper complexes                                                              __________________________________________________________________________                                        Specific*                                                                             Elemental analysis**              Exam-                   Yield                                                                             m.p.    rotation                                                                              C    H   N    Cu                  ple      Compound       (%) (° C.)                                                                         (deg.)  (%)  (%) (%)  (%)                 __________________________________________________________________________        (R)-N-salicylidene-2-amino-                                               2A  1,1-di(2-butoxy-5-t-butyl-                                                                        90  oil     --      --   --   --   --                     phenyl)-3-phenyl-1-propanol                                                   Copper complex of the above     +1040   72.91                                                                              7.71                                                                              1.98 8.56                2B  Schiff base         72  --      (benzene)                                                                             (72.85                                                                             7.64                                                                              1.93 8.76)                   (S)-N-salicylidene-2-amino-     -65.2   76.83                                                                              6.23                                                                              2.81  --                 3A  1,1-di(2-methoxyphenyl)-3-                                                                        70  80.9    (chloroform)                                                                          (77.06                                                                             6.25                                                                              3.00)                        phenyl-1-propanol                                                             Copper complex of the   150     -1500   68.73                                                                              5.35                                                                              2.61 11.98               3B  above Schiff base   70  (dec.)  (toluene)                                                                             (68.10                                                                             5.14                                                                              2.65 12.01)                  (S)-N-salicylidene-2-amino-                                               4A  1,1-di(2-ethoxyphenyl)-3-                                                                         85  oil     --      --   --   --   --                     phenyl-1-propanol                                                             Copper complex of the           -1240   69.13                                                                              5.44                                                                              2.72 11.50               4B  above Schiff base   79  --      (ethanol)                                                                             (68.99                                                                             5.61                                                                              2.51 11.41)                  (S)-N-salicylidene-2-amino-     -60.3   78.42                                                                              7.53                                                                              2.60 --                  5A  1,1-di(2-butoxyphenyl)-3-                                                                         85  119-121 (chloroform)                                                                          (78.37                                                                             7.49                                                                              2.54)                        phenyl-1-propanol                                                             Copper complex of the           -1170   70.19                                                                              6.50                                                                              2.21 11.35               5B  above Schiff base   92  --      (ethanol)                                                                             (70.50                                                                             6.41                                                                              2.28 10.36)                  (R)-N-salicylidene-2-amino-     +52.8   80.73                                                                              9.17                                                                              2.06                     6A  1,1-di(2-octyloxyphenyl)-3-                                                                       67  --(chloroform)                                                                        (79.60  8.65 2.11                                                                               --                          phenyl-1-propanol                                                             Copper complex of the           +1140   72.61                                                                              7.82                                                                              1.69 6.99                6B  above Schiff base   88  --      (benzene)                                                                             (72.85                                                                             7.64                                                                              1.93 8.76)                   (R)-N-salicylidene-2-amino-     +57.9   81.07                                                                              5.66                                                                              2.40                     7A  1,1-di(2-phenoxyphenyl)-3-                                                                        93  150.4   (chloroform)                                                                          (81.19                                                                             5.62                                                                              2.37  --                     phenyl-1-propanol                                                             Copper complex of the           +953    73.38                                                                              5.24                                                                              2.38 9.17                7B  above Schiff base   67  --       (benzene)                                                                            (73.55                                                                             4.78                                                                              2.14 9.73)                   (S)-N-salicylidene-2-amino-                                                   1,1-di(2-benzyloxy-5-                                                     8A  methylphenyl)-3-phenyl-                                                                           80  oil     --      --   --   --   --                     1-propanol                                                                Copper complex of the       -1830   74.54   5.62 2.09                                                                              8.22                     8B  above Schiff base   88  --      (benzene)                                                                             (74.50                                                                             5.54                                                                              1.98 8.96)                   (S)-N-salicylidene-2-amino-                                                   1,1-di(5-t-butyl-2-isopro-                                                9A  poxyphenyl)-3-phenyl-1-                                                                           80  oil     --      --   --   --   --                     propanol                                                                      Copper complex of the           -973    71.98                                                                              7.53                                                                              2.10 9.11                9B  above Schiff base   45  --      (benzene)                                                                             (72.33                                                                             7.37                                                                              2.01 9.11)                   (R)-N-salicylidene-2-amino-                                                   1,1-di(5-t-butyl-2-octyloxyphenyl)-                                       10A 3-phenyl-1-propanol 80  oil     --      --   --   --   --                     Copper complex of the above     +730    74.71                                                                              8.85                                                                              1.73 7.13                10B Schiff base         65  --      (benzene)                                                                             (74.56                                                                             1.67                                                                              7.59)                        (R)-N-salicylidene-2-amino-     +62     82.24                                                                              7.43                                                                              1.98                     11A 1,1-di(4-butoxybiphenyl-3-                                                                        77  114.8   (chloroform)                                                                          (81.90                                                                             7.02                                                                              1.99  --                     yl)-3-phenyl-1-propanol                                                       Copper complex of the           +1730   75.96                                                                              6.59                                                                              1.83 8.79                11B above Schiff base   50  --      (benzene)                                                                             (75.32                                                                             6.19                                                                              1.83 8.30)                   (R)-N-salicylidene-2-amino-                                               12A 1,1-di(2,5-dibutoxyphenyl)-                                                                       85  oil     --      --   --   --   --                     3-phenyl-1-propanol                                                           Copper complex of the           +1140   70.41                                                                              7.53                                                                              1.67 7.60                12B above Schiff base   50  --      (benzene)                                                                             (69.72                                                                             7.31                                                                              1.85 8.38)                   (S)-N-salicylidene-2-amino-                                               13  1,1-di(2-isopropoxyphenyl)-3-                                                                     85  oil     --      --   --   --   --                     (4-isopropoxyphenyl)-1-                                                       propanol                                                                      Copper complex of the           -1210   68.34                                                                              6.53                                                                              1.56 9.74                13B above Schiff 45     --  (benzene)                                                                             (69.08  6.42 2.18                             (S)-N-salicylidene-2-amino-                                                   1,1-di(5-t-butyl-2-octyloxyphenyl)-                                       14A 3-(4-ispropoxyphenyl)-1-                                                                          80  oil     --      --   --   --   --                     propanol                                                                      Copper complex of the   - 74.66 8.86    1.29 7.22                         14B above Schiff base   70  --      (benzene)                                                                             (75.09                                                                             8.82                                                                              1.59 7.22)                   (S)-N-salicylidene-2-amino-                                               15A 1,1-di(2-butoxyphenyl)-3-                                                                         95  oil     --      --   --   --   --                     cyclohexyl-1-propanol                                                         Copper complex of the           -814    68.48                                                                              7.61                                                                              2.20 8.99                15B above Schiff base   93  --      (benzene)                                                                             (69.82                                                                             7.32                                                                              2.26 10.26)                  (S)-N-salicylidene-2-amino-     +165    74.62                                                                              7.12                                                                              3.04  --                 16A 1,1-di(2-methoxyphenyl)-                                                                          65  142.0   (chloroform)                                                                          (74.80                                                                             7.21                                                                              3.23)                        4-methyl-1-pentanol                                                           Copper complex of the           -1110   65.59                                                                              6.10                                                                              2.71 12.17               16B above Schiff base   70  --      (benzene)                                                                             (65.50                                                                             5.91                                                                              2.83 12.83)                  (S)-N-salicylidene-2-amino-                                                   1,1-di(2-butoxy-5-t-butyl-                                                17A phenyl)-4-methyl-1- 80  oil     --      --   --   --   --                     Copper complex of the           -540    70.98                                                                              8.61                                                                              2.20 8.70                17B Schiff base         87  --      92      (71.22                                                                             8.31                                                                              2.03 9.19)                   (S)-N-salicylidene-2-amino-                                               18A 1,1-di(2-benzyloxy-5-t-butyl-                                                                     90  oil     --      --   --   --   --                     phenyl)-4-methyl-1-pentanol                                                   Copper complex of the           -500    74.20                                                                              7.04                                                                              1.62 8.58                18B above Schiff base   80  --      (benzene)                                                                             (74.33                                                                             7.03                                                                              1.84 8.37)                   (S)-N-salicylidene-2-amino-                                               19A 1,1-di(2-butoxy-5-t-butyl-                                                                        90  oil     --      --   --   --   --                     phenyl)-1-propanol                                                            Copper complex of the           -682    70.73                                                                              8.37                                                                              2.27 8.50                19B above Schiff base   92  --      (benzene)                                                                             (70.56                                                                             7.84                                                                              2.14 9.70)                   (S)-N-salicylidene-2-amino-                                               20A 1,1-di(2-butoxyphenyl)-3-                                                                         92  oil     --      --   --   --   --                     methyl-1-butanol                                                              Copper complex of the           -929    66.82                                                                              7.15                                                                              2.31 11.3                20B above Schiff base   91  --      (benzene)                                                                             (66.58                                                                             7.26                                                                              2.59 11.74)                  (S)-N-salicylidene-2-amino-     +87.8   75.58                                                                              7.92                                                                              2.91  --                 21A 1,1-di(2-butoxyphenyl)-3-                                                                         93  112- 113                                                                              (chloroform)                                                                          (75.76                                                                             7.84                                                                              2.94)                        propanol                                                                      Copper complex of the           -1077   71.38                                                                              6.93                                                                              2.88 12.40               21B above Schiff base   90  --      (benzene)                                                                             (71.76                                                                             7.03                                                                              2.79 12.65)                  (R)-N-(3,5-dibromosali-                                                       cylidene)-2-amino-1,1-                                                    22A di(2-isopropoxyphenyl)-3-                                                                         90  oil     --      --   --   --   --                     phenyl-1-propanol                                                             Copper complex of the           +840    55.41                                                                              4.63                                                                              1.99 7.17                22B above Schiff base   86  --      (ethanol)                                                                             (54.96                                                                             1.89                                                                              8.55)                        (R)-N-(3-ethoxysali-                                                          cylidene)-2-amino-1,1-                                                    23A di(2-isopropoxyphenyl)-                                                                           90  oil     --      --   --   --   --                     3-phenyl-1-propanol                                                           Copper complex of the           +1140   68.27                                                                              6.26                                                                              2.22 9.88                23B above Schiff base   90  --      (ethanol)                                                                             (68.72                                                                             6.25                                                                              2.23 10.10)                  (R)-N-(2-hydroxy-1-                                                           naphthylemethylene)-2-                                                    24A amino-1,1-di(2-isopro-                                                                            90  oil     --      --   --   --   --                     poxyphenyl)-3-phenyl-1-                                                       propanol                                                                      Copper complex of the           +1180   71.98                                                                              6.04                                                                              2.29 8.78                24B above Schiff base   49  --      (ethanol)                                                                             (71.85                                                                             5.87                                                                              2.20 10.00)                  N-salicylidene(S)-2-                                                          amino-1,1-di(2-3'-oxa-                                                    25A pentoxy-5-t-butyl   80  oil             --   --   --   --                     phenyl)-1-propanol                                                            Copper complex of the           -300    67.33                                                                              7.12                                                                              2.31 9.50                25B above Schiff base   85  --              (66.99                                                                             7.54                                                                              2.06 9.33)                   N-salicylidene(S)-2-                                                          amino-1,1-di(2-cyclo-           +155    79.10                                                                              8.90                                                                              2.00  --                 26A hexyloxy-5-t-butyl- 90  78.6            (78.87                                                                             8.92                                                                              2.19)                        phenyl)-1-propanol                                                            Copper complex of the   160°-848                                                                       72.10   8.12 2.13                                                                              10.00                    26B above Schiff base   90  (dec.)  (71.95  7.85 2.00                                                                              9.07)                        N-salicylidene(R)-2-                                                          amino-1,1-di(2-cyclo-                                                     27A hexyloxy-5-t-butyl- 85  oil     --      --   --   --   --                     phenyl)-3-phenyl-1-                                                           propanol                                                                      Copper complex of the           +697    75.21                                                                              7.51                                                                              2.23 9.37                27B above Schiff base   80  150°     (74.18                                                                             7.60                                                                              1.80 8.18)                   N-salicylidene(S)-2-                                                          amino-1,1-di(2-t-butoxy-                                                  28A 5-t-butylphenyl)-1- 85  oil     --      --   --   --   --                     propanol                                                                      Copper complex of the           -510    69.21                                                                              7.94                                                                              2.29 9.14                28B above Schiff base   42  --              (70.56                                                                             7.84                                                                              2.14 9.70)                   N-salicylidene(S)-2-                                                          amino-1,1-di(2-iso-                                                       29A propoxy-5-methylphenyl                                                                            90  oil     --      --   --   --   --                     1-propanol                                                                    Copper complex of the           -1090   67.16                                                                              6.83                                                                              2.62 12.89               29B above Schiff base   99  --              (67.08                                                                             6.57                                                                              2.61 11.83)                  N-salicylidene(S)-2-                                                          amino-1,1-di(2-benzyl-                                                    30A oxy-4-t-butylphenyl 80  oil     --      --   --   --   --                     1-propanol                                                                    Copper complex of the           -590    75.74                                                                              6.63                                                                              2.15 7.68                30B above Schiff base   39  --              (73.67                                                                             6.60                                                                              1.95 8.86)                   N-salicylidene(S)-2-                                                          amino-1,1-di(2-sec-butoxy-                                                31A 5-t-butylphenyl)-1- 80  oil     --      --   --   --   --                     propanol                                                                      Copper complex of the           -1000   69.56                                                                              8.29                                                                              2.42 9.53                31B above Schiff base   75  --              (70.29                                                                             7.92                                                                              2.16 9.79)                   N-salicylidene(S)-2-                                                          amino-1,1-di(2-                                                           32A benzyloxy-5-t-butyl-                                                                              85  oil     --      --   --   --   --                     phenyl)-1-propanol                                                            Copper complex of the           -533    74.15                                                                              6.90                                                                              1.94 8.30                32B -1380               Schiff base                                                                       32      --      (73.67                                                                             6.60                                                                              1.95 8.86)                   N-salicylidene(S)-2-                                                          amino-1,1-di(2-butoxy-                                                    33A 4-t-butylphenyl)-1- 85  oil     --      --   --   --   --                     propanol                                                                      Copper complex of the           -274    70.55                                                                              8.10                                                                              2.03 10.21               33B above Schiff base   87  --              (70.29                                                                             7.92                                                                              2.16 9.79)                   N-salicylidene(S)-2-                                                          amino-1,1-di(2,5-                                                         34A dibutoxyphenyl)-1-  92  69-71   +969    --   --   --   --                     propanol                                                                      Copper complex of the           -1380   67.37                                                                              7.96                                                                              2.44 10.1                34B                                                                               above Schiff base   73  --              (68.49                                                                             7.87                                                                              2.10 9.54)                   N-salicylidene(S)-2-                                                          amino-1,1-di(4-octyloxy-        +70.1   79.77                                                                              8.64                                                                              1.64  --                 35A 3-biphenyl)-1-      76  128-129          (81.15                                                                            8.31                                                                              1.89)                        propanol                                                                      Copper complex of the           -1498   75.54                                                                              7.80                                                                              1.67 9.50                35B                                                                               above Schiff base   98  --              (74.92                                                                             7.42                                                                              1.75 7.93)                   N-salicylidene(S)-2-            +73.3   79.87                                                                              7.53                                                                              2.15  --                 36A amino-1,1-di(4-butoxy-3-                                                                          93  169.5-170.5     (80.35                                                                             7.22                                                                              2.23)                        biphenyl)-1-propanol                                                          Copper complex of the                   70.79                                                                              6.56                                                                              1.60 8.90                36B above Schiff base   93  --      --      (73.18                                                                             6.29                                                                              2.03 9.22)                   N-salicylidene(S)-2-                                                          amino-1,1-di(5-t-butyl-                                                   37A 2-octyloxyphenyl)-  98  oil     -25.5   --   --   --   --                     1-propanol                                                                    Copper complex of the           -550    72.12                                                                              8.90                                                                              2.13 8.50                37B above Schiff base   86  --              (72.55                                                                             8.87                                                                              1.84 8.34)                   N-salicylidene(S)-2-                                                          amino-1,1-di(2-     79  119-125 +91.3   76.74                                                                              8.32                                                                              2.74  --                 38A butoxy-5-methylphenyl)-                 (76.31                                                                             8.20                                                                              2.78)                        1-propanol                                                                    Copper complex of the                   65.25                                                                              7.66                                                                              2.40 10.2                38B                                                                               above Schiff base   97  --      -1352   (68.00                                                                             6.96                                                                              2.48 11.24)                  N-salicylidene(S)-2-                                                          amino-1,1-di(2-butoxy-                                                    39A 5-t-butylphenyl)-3- 90  oil     --      --   --   --   --                     (4-benzyloxyphenyl)-                                                          1-propanol                                                                    Copper complex of the                   74.47                                                                              7.83                                                                              1.46 6.37                39B Above Schiff base   80  --      -690    (73.66                                                                             7.39                                                                              1.68 7.64)                   N-salicylidene(S)-2-                                                          amino-1,1-di(2-butoxy-                                                    40A 5-t-butylphenyl)-3- 80  oil     --      --   --   --   --                     methyl-1-butanol                                                              Copper complex of the                   70.37                                                                              8.70                                                                              2.04 9.54                40B above Schiff base   88  --      -789    (70.92                                                                             8.18                                                                              2.07 9.38)                   N-salicylidene(S)-2-                                                          amino-1,1-di(2-butoxy-                                                    41A phenyl)-4-methyl-1- 88  oil     --      --   --   --   --                     pentanol                                                                      Copper complex of the                   69.51                                                                              7.94                                                                              2.64 9.40                41B above Schiff base   99  --      -647    (68.43                                                                             7.12                                                                              2.42 10.97)              __________________________________________________________________________     Note:                                                                         * Specific rotations are shown as [α].sub.D (chloroform) for Schiff     bases and as [α].sub.546 (benzene) for copper complexes unless          otherwise specified.                                                          **Calculated values are shown in parentheses.                            

EXAMPLE 42C

To millimols) suspension of 0.43 g. (1.4 millimoles ofbis(salicylaldehydate)copper in 10 ml. methanol was added dropwise asolution of 1.1 g. (3.0 millimols) of(R)-2-amino-1,1-di(2-methoxyphenyl)-3-phenyl-1-propanol {[α]_(D) +42.3°(c 1.1, chloroform)} in 10 ml. of methanol. The addition was carried outunder thorough stirring at room temperature. The period of the additionwas one hour and the reaction mixture was stirred for another one hour.The resulting solids were collected by filtration, washed with methanoland dried under reduced pressure to give a mononuclear complex of(R)-N-salicylidene-2-amino-1,1-di(2-methoxyphenyl)-3-phenyl-1-propanolas grayish blue crystals. Yield, 0.75 g. (58%), [α]₅₄₆, +860° (c 0.065,benzene), melting point: 205° - 206° C. (decomposed).

    ______________________________________                                        Elemental analysis for C.sub.60 H.sub.56 CuN.sub.2 O.sub.8                                C (%)     H (%)    N (%)  Cu (%)                                  Found:      71.87     5.57     3.00   5.82                                    Calculated: 72.31     5.66     2.81   6.38                                    Magnetic susceptibility μ = 1.78 B.M.                                      ______________________________________                                    

EXAMPLES 43C and 44C

In a similar manner to Example 42C, other two kinds of chiralmononuclear copper complexes of the formula (III) were synthesized fromchiral amino alcohols of the formula (IV) and bis(salicylaldehydato)copper. The results are summarized in Table 4.

                                      Table 4                                     __________________________________________________________________________    Chiral mononuclear copper complexes                                           __________________________________________________________________________                                 Specific*                                                                           Elemental analysis**                       Exam-                Yield                                                                             m.p.                                                                              Rotation                                                                            C    H   N   Cu                            ple      Compound    (%) (° C.)                                                                     (deg) (%)  (%) (%) (%)                           __________________________________________________________________________        Mononuclear copper complex of                                                 (R)-N-salicylidene-2-          71.22                                                                              5.23                                                                              2.60                                                                              6.52                          43C amino-1,1-di(3-methoxy-                                                                        50  --  --    (72.31                                                                             5.66                                                                              2.81                                                                              6.38)                             phenyl)-3-phenyl-1-                                                           propanol                                                                      Mononuclear copper complex                                                    of (S)-N-salicylidene-2- -620  69.12                                                                              6.37                                                                              2.92                                                                              7.42                          44C amino-1,1-di(2-methoxyphenyl)-                                                                 60  --  (benzene)                                                                           (69.84                                                                             6.51                                                                              3.02                                                                              6.84)                             4-methyl-1-pentanol                                                       __________________________________________________________________________     Note: *  Specific rotations are shown as [α].sub.D for Schiff based     and as [α].sub.564 for copper complexes. Solvents are shown in          parentheses.                                                                  **Calculated values are shown in parentheses.                            

What we claim is:
 1. A process for the production of an optically activealkyl chrysanthemate which comprises reacting 2,5-dimethyl-2,4-hexadienewith an alkyl diazoacetate in the presence of a copper complexcoordinated with a chiral Schiff base at a temperature in the range of-50° C to 150° C, said Schiff base having the formula: ##STR7## whereinC* is an asymmetric carbon atom, R¹ is selected from the groupconsisting of (a) alkyl groups whose carbon atom number is 1 - 10, and(b) aralkyl groups with or without alkoxy substituent(s), whose totalcarbon atom number is 7 - 20, R² is selected from aryl groups withalkoxy substituent(s), whose total carbon atom number is 7 -30, X may besubstituted at 1 or 2 positions on the ring and is selected from thegroup consisting of (a) alkyl having 1 - 10 carbon atoms, (b) phenyl,(c) benzo, (d) alkoxy having 1 - 10 carbon atoms, (e) halogen and (f)nitro, and Y is a hydrogen atom and wherein the molar ratio of the saidcopper complex to alkyl diazoacetate is in the range of 0.001 -0.1. 2.The process of claim 1 in which said copper complex has the followingstructure: ##STR8## wherein R¹, R², X and Y are defined as in claim 1.3. The process of claim 1 in which said copper complex has the followingstructure: ##STR9## wherein C*, R¹, R², X and Y are defined as inclaim
 1. 4. The process of claim 1 in which said chiral Schiff base isprepared by the reaction of a chiral amino alcohol of the formula:##STR10## wherein C*, R¹ and R² are defined as in claim 1, and asalicylaldehyde derivative of the formula: ##STR11## wherein X and Y aredefined as in claim
 1. 5. The process of claim 2 in which said coppercomplex is prepared by the reaction of a chiral Schiff base of Claim 4with a cupric salt.
 6. The process of claim 3 in which said coppercomplex is prepared by the reaction of a chiral amino alcohol of Claim 4with a copper complex of salicylaldehyde derivative of Claim
 4. 7. Theprocess of claim 1 in which R¹ isa. benzyl, b. 4-methoxyphenylmethyl, c.4-isopropoxyphenylmethyl, d. 4-butoxyphenylmethyl, e.4-benzyloxyphenylmethyl, f. methyl, g. isopropyl, h. isobutyl, or i.cyclohexylmethyl.
 8. The process of claim 4 in which saidsalicylaldehyde derivative isa. salicylaldehyde, b.3,5-dibromosalicylaldehyde, c. 3-ethoxysalicylaldehyde, or d.2-hydroxy-1-naphthaldehyde.
 9. The process of claim 3 in which saidchiral Schiff base is either a (R)- or (S)-enantiomer of thefollowing:a.N-salicylidene-2-amino-1,1-di(2-methoxyphenyl)-3-phenyl-1-propanol, b.N-salicylidene-2-amino-1,1-di(3-methoxyphenyl)-3-phenyl-1-propanol, orc. N-salicylidene-2-amino-1,1-di(2-methoxyphenyl)-4-methyl-1-pentanol.10. The process according to claim 1, wherein the alkyl group of saidalkyl diazoacetate is a lower aliphatic alkyl.
 11. The process accordingto claim 1, wherein the reaction is conducted in the presence of asolvent.
 12. The process according to claim 11, wherein said solvent isan aromatic hydrocarbon.
 13. A process for the production of anoptically active alkyl chrysanthemate which comprises reacting2,5-dimethyl-2,4-hexadiene with an alkyl diazoacetate in the presence ofa copper complex coordinated with a chiral Schiff base at a temperaturein the range of -50° C, said Schiff base having the formula: ##STR12##wherein C* is an asymmetric carbon atom, R¹ is selected from the groupconsisting of (a) alkyl groups whose carbon atom number is 1 - 10, and(b) aralkyl groups with or without alkoxy substituent(s), whose totalcarbon atom number is 7 - 20, R² is (a) 2-methoxyphenyl, (b)2-ethoxyphenyl, (c) 2-isopropoxyphenyl, (d) 2-butoxyphenyl, (e)2-octyloxyphenyl, (f) 2-benzyloxy-5-methylphenyl, (g)2-butoxy-5-t-butylphenyl, (h) 5-t-butyl-2-octyloxyphenyl, (i)4-butoxybiphenyl-3-yl, or (j) 2,5-dibutoxyphenyl, and Y is a hydrogenatom and wherein the molar ratio of the said copper complex to alkyldiazoacetate is in the range of 0.001 - 0.1.
 14. A process for theproduction of an optically active alkyl chrysanthemate which comprisesreacting 2,5-dimethyl-2,4-hexadiene with an alkyl diazoacetate in thepresence of a copper complex coordinated with a chiral Schiff base at atemperature in the range of -50° C to 150° C, said chiral Schiff basebeing either an (R)- or (S)-enantiomer of the following:a.N-salicylidene-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl-1-propanol,b.N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butylphenyl)-3-phenyl-1-propanol,c. N-salicylidene-2-amino-1,1-di(2-methoxy-phenyl)-3-phenyl-1-propanol,d. N-salicylidene-2-amino-1,1-di(2-ethoxyphenyl)-3-phenyl-1-propanol, e.N-salicylidene-2-amino-1,1-di(2-butoxyphenyl)-3-phenyl-1-propanol, f.N-salicylidene-2-amino-1,1-di(2-octyloxyphenyl)-3-phenyl-1-propanol, g.N-salicylidene-2-amino-1,1-di(2-phenoxyphenyl)-3-phenyl-1-propanol, h.N-salicylidene-2-amino-1,1-di(2-benzyloxy-5-methylphenyl)-3-phenyl-1-propanol,i.N-salicylidene-2-amino-1,1-di(5-t-butyl-2-isopropoxyphenyl)-3-phenyl-1-propanol,j.N-salicylidene-2-amino-1,1-di(5-t-butyl-2-octyloxyphenyl)-3-phenyl-1-propanol,k.N-salicylidene-2-amino-1,1-di(4-butoxybiphenyl-3-yl)-3-phenyl-1-propanol,l.N-salicylidene-2-amino-1,1-di(2,5-dibutoxyphenyl)-3-3-phenyl-1-propanol,m.N-salicylidene-2-amino-1,1-di(2-isopropoxyphenyl)-3-(4-isopropoxyphenyl)-1-propanol,n.N-salicylidene-2-amino-1,1-di(5t-butyl-2-octyloxyphenyl)-3-(4-isopropoxyphenyl)-1-propanol,o.N-salicylidene-2-amino-1,1-di(2-butoxyphenyl)-3-cyclohexyl-1-propanol,p. N-salicylidene-2-amino-1,1-di(2-methoxyphenyl)-4-methyl-1-pentanol,q.N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butylphenyl)-4-methyl-1-pentanol,r.N-salicylidene-2-amino-1,1-di(2-benzyloxy-5-t-butylphenyl)-4-methyl-1-pentanol,s. N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butylphenyl)-1-propanol,t. N-salicylidene-2-amino-1,1-di(2-butoxyphenyl)-3-methyl-1-butanol, u.N-salicylidene-2-amino-1,1-di(2-butoxyphenyl)-1-propanol, v.N-(3,5-dibromosalicylidene)-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl-1-propanol,w.N-(3-ethoxysalicylidene)-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl-1-propanol,x.N-(2-hydroxy-1-naphthylmethylene)-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl-1-propanol,or y. N-salicylidene-2-amino-1,1-di(4-butoxybiphenyl-3-yl)-1-propanol,and wherein the molar ratio of said copper complex to the alkyldiazoacetate is in the range of 0.001 - 0.1.
 15. The process accordingto claim 14, wherein the alkyl group of said alkyl diazoacetate is alower aliphatic alkyl.
 16. The process according to claim 14, whereinthe reaction is conducted in the presence of a solvent.
 17. The processaccording to claim 16, wherein said solvent is an aromatic hydrocarbon.